US3816378A - Polyester salts containing quaternary ammonium groups - Google Patents

Polyester salts containing quaternary ammonium groups Download PDF

Info

Publication number
US3816378A
US3816378A US00369076A US36907673A US3816378A US 3816378 A US3816378 A US 3816378A US 00369076 A US00369076 A US 00369076A US 36907673 A US36907673 A US 36907673A US 3816378 A US3816378 A US 3816378A
Authority
US
United States
Prior art keywords
polyester
acid
salts
percent
washing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00369076A
Other languages
English (en)
Inventor
E Schmadel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to DE19702054097 priority Critical patent/DE2054097A1/de
Priority to NL7113785A priority patent/NL7113785A/xx
Priority to AT947371A priority patent/AT314052B/de
Priority to CH1601271A priority patent/CH562317A5/xx
Priority to FR7139526A priority patent/FR2112453B1/fr
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to US00369076A priority patent/US3816378A/en
Application granted granted Critical
Publication of US3816378A publication Critical patent/US3816378A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
    • C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents

Definitions

  • This invention relates to polyester salts containing quaternary ammonium groups, obtainable by polycon- [30] Foreign Application priority Data densation of N-alkyl-dialkanolamines with dicarbox- N 4 1970 G 2054097 ylic acids, particularly maleic acid, and quaternization many of the polyester with a haloacetic acid. Additional sulfonic acid groups can be introduced into the polyester [52] Cl gig jig molecule by reaction with an alkali metal hydrogen [5!] In Cl (5088 17/12 2:088 17/04 sulfite.
  • polyester salts are utilized as soil suspen- 58 Field 260/75 N, 4 85 0, 481 R gems washmg 6 Claims, No Drawings POLYESTER SALTS CONTAINING QUATERNARY AMMONIUM GROUPS This is a continuation, of Ser. No. l88,940, filed Oct. l3, l9 nowadays and now abandoned.
  • carboxymethylcellulose has, of the compounds considered, obtained any great technical importance, particularly as it surpasses, in its greying-inhibiting efiect, numerous known synthetic polymers.
  • Carboxymethylcellulose and also the other synthetic polymers named have, however, the disadvantage that their greying-preventing effect is limited to cellulosic fibers. They are largely ineffective in the washing of synthetic fiber materials, chemically changed cellulose or finished cotton. This disadvantage is particularly observable in white textiles from polyester or polyolefin fibers, non-iron finished cotton and in mixed fabrics of the so-called synthetic fibers with cellulose fibers, which become grey, in spite of frequent washing, and thus become unattractive.
  • An object of the present invention is the development of a soil suspension agent which avoids the drawbacks of the prior art agents and which is effective with textiles of synthetic fibers.
  • Another object of the present invention is the development of a polyester salt, containing quaternary ammonium groups. suitable for use in washing agents as a soil suspension agent, having the formula omcoo i 8 wherein R represents a hydrocarbon with 6 to 24 carbon atoms, R" represents a divalent linkage selected from the group consisting of R, where R represents a hydrocarbon with l to 10 carbon atoms,
  • Me represents a metal selected from the group consisting of sodium and potassium
  • n represents the integers 2, 3 or 4
  • x represents a whole number from 5 to 5,000.
  • a further object of the invention is the development of a process for cleansing textiles which comprises immersing soiled textiles in a conventional neutral to alkaline aqueous washing liquor bath containing from 0.005 to l gm/liter of the above polyester salt, containing quaternary ammonium groups, for a time sufiicient DESCRIPTlON OF THE INVENTION
  • the above objects have been achieved and the drawbacks of the prior art overcome by the development of polyester salts, containing quaternary ammonium groups which effect suspension of soil in textile washing bath liquors.
  • the invention relates to polyester salts, containing quaternary ammonium groups, suitable for the use in washing agents, characterized by the formula in which R represents a hydrocarbon radical with 6 to 24 carbon atoms, R represents a hydrocarbon radical with l to 10 carbon atoms, Me represents sodium or potassium, x represents a whole number from 5 to 5,000, n represents the numbers 2, 3, or 4 and y any number from 0 to 1 including fractional numbers.
  • y represents a fractional number the polyester molecule contains both the dicarboxylic acid moiety and the sulfosuccinic moiety.
  • the polyester salts of the invention are a polyester salt, containing quaternary ammonium groups, suitable for use in washing agents as a soil suspension agent, having the formula wherein R represents a hydrocarbon with 6 to 24 carbon atoms, R" represents a divalent linkage selected from the group consisting of R, where R represents a hydrocarbon with l to 10 carbon atoms,
  • Me represents a metal selected from the group consisting of sodium and potassium
  • n represents the integers 2, 3 or 4
  • x represents a whole number from 5 to 5,000.
  • R is a hydrocarbon having 6 to 24 carbon atoms, preferably 10 to carbon atoms, selected from the group consisting of alkyl, alkenyl, phenyl, phenylalkyl, alkylphenyl, cycloalkyl, cycloalkylalkyl and alkylcycloalkyl;
  • R is a divalent hydrocarbon having l to 10 carbon atoms preferably selected from the group consisting of alkylene, alkenylene, phenylene, alkylphenylene, cyclohexylene and cyclohexenylene; and
  • C,,H,, represents, preferably, ethylene, propylene, isopr'opylene, butylene and isobutylene.
  • the N-substituted dialkanolamine radicals contained in the above-named polyester salts, are derived, for example, from dipropanolamine, diisopropanolamine or dibutanolamine, however, particularly from diethanolamine and have on the nitrogen atom an aliphatic, cycloaliphatic or aromatic hydrocarbon radical, however, preferably a straight-chain alkyl radical with 6 to 24 and particularly 10 to 20 carbon atoms. Examples for such alkyls are hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and eicosyl. Also mixtures of N-alkylated dialkanolamines, that have different alkyl groups, are usable as starting substances.
  • polyester salts contain both the above-named dicarboxylic acid radicals and the sulfosuccinic acid radi' cals, the molar ratio of these radicals to each other may have any value.
  • polyester salts that are derived from N-alkylated diethanolamines and maleic acid or their sulfonation products.
  • polyester salts are such of the formulae omooo o in which R and Me have the above-named meanings.
  • the preparation of the polyester salts, according to the invention can be carried out in a known manner by esterification of the monomeric starting compounds, quaternization of the obtained polyester with the aid of a haloacetic acid, such as chloroacetic or bromoacetic acid and, if necessary, sulfonation of the olefmic double bonds, contained in the maleic acid moieties.
  • a haloacetic acid such as chloroacetic or bromoacetic acid
  • the esterification of the reaction components is performed, for instance, by heating for several hours under normal pressure, under vacuum or in the presence of a solvent with which the reaction water can be distilled ofi' azeotropically.
  • the reaction can be speeded up by the addition of conventional esterification catalysts, particularly of strong inorganic or organic acids, such as sulfuric acid or p-toluenesulfonic acid. lnstead of the free dicarboxylic acids, their reactive derivatives, such as anhydrides or halides may also be charged as starting compounds.
  • the dicarboxylic acids in the form of their dimethyl or diethyl esters can be transesterified with the dialkanolamines in the presence of customary transesterification catalysts in a known manner.
  • the quaternization of the polyester with the aid of salts, particularly sodium or potassium salts of haloacetic acids, such as monochloroacetic acid or monobromoacetic acid can be carried out in the melt or in the presence of solvents.
  • the reaction is carried out by suspending the polyester in water and, after addition of the chloroacetate or bromoacetate, heating until the polyester is completely dissolved, whereby the termination of the reaction is indicated.
  • sulfonate groups are to be inserted into the polyester molecule, a portion of maleic acid is employed and this is done appropriately by addition of sodium or potassium bisulfite to the double bond of the maleic acid moiety.
  • This reaction is appropriately carried out in an aqueous medium, optionally also in the presence of free radical catalysts, such as peroxides.
  • free radical catalysts such as peroxides.
  • the reaction is carried out with a certain excess of sulfonation agents, in order to attain as complete a reaction as possible.
  • bisulfite instead of the bisulfite other sulfonation agents may be used, such as complex compounds of sulfur trioxide and dioxan, pyridine, or N,N-dimethylaniline. It is also possible to carry out the sulfonation of the polyester before the quaternization reaction.
  • polyester salts containing quaternary ammonium groups or optionally sulfonate groups of the invention have a resin-like consistency and are insoluble in organic solvents, but easily soluble in water. They may also contain subordinate amounts of lower molecular weight esters or of unreacted starting materials. These can be removed by extraction with organic solvents and optionally again reacted. Since these byproduct compounds do, however, not impair the cleaning properties of the agents, a separation is generally not required.
  • the average degree of polymerization of the polyester salts which corresponds in the preceding formulae to the number x, is preferably between 10 and 1,000.
  • the preferred field of application of the novel polyester salts are in washing agent compositions that contain surface-active, wash-active compounds, such as anionic, non-ionic and amphoteric detergents, and nonsurface-active builder salts, such as condensed phosphates, sequestering agents and washing alkalis and optionally auxiliaries and supplements customary in washing agent formulations.
  • surface-active, wash-active compounds such as anionic, non-ionic and amphoteric detergents
  • nonsurface-active builder salts such as condensed phosphates, sequestering agents and washing alkalis and optionally auxiliaries and supplements customary in washing agent formulations.
  • Suitable washing raw materials are anionic surfaceactive compounds, such as of the sulfonate or the sulfate type, for instance, alkylbenzenesulfonates, particularly n-dodecylbenzenesulfonate, also olefin sulfonates, as they are obtained, for instance, by sulfonation of primary or secondary aliphatic monoolefins with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis, as well as alkylsulfonates as they are obtainable from n-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins.
  • Suitable are also oz-sulfofatty acid esters, primary and secondary alkylsulfates as well as the sulfates of ethoxylated or propoxylated higher molecular weight alcohols.
  • Further compounds of this class of anionic surfaceactive compounds that can optionally be present in the washing agents, are the higher molecular sulfated partial ethers and partial esters of polyhydric alcohols, such as the alkali metal salts of the monoalkyl ethers or of the monofatty acid esters of glycerinmonosulfuric acid ester or of the l,Z-dihydroxypropanesulfonic acid. Furthermore, the sulfates of ethoxylated or propoxylated fatty acid amides and alkylphenols as well as fatty acid taurides and fatty acid isothionates are suitable.
  • anionic washing raw materials are alkali metal soaps of fatty acids of natural or synthetic origin, such as the sodium soaps of coconut, palm kernel or tallow fatty acids.
  • amphoteric washing raw materials are amphoteric surface-active compounds,
  • alkylbetaines and particularly the alkylsulfobetaines such as the 3-(N,N-dimethyl-N- alkylammonium)-propane-l-sulfonate and the 3-(N,N- dimethyl-N-alkylammonium )-2-hydroxypropanel sulfonate where the alkyl has from 6 to 24 carbon ato-
  • the anionic washing raw materials may be present in the form of alkali metal salts, such as sodium and potassium, and ammonium salts as well as salts of organic bases, such as mono-, dior triethanolamine.
  • anionic and amphoteric compounds have an aliphatic hydrocarbon radical
  • the latter should preferably have a straight chain with 8 to 22 carbon atoms.
  • the compounds with an araliphatic hydrocarbon radical preferably these are alkylphenyls having an unbranched alkyl chain of 6 to l6 carbon atoms.
  • polyglycolether derivatives of alcohols fatty acids and alkylphenols are suitable that contain 3 to 30 glycolether groups, preferably ethyleneglycol ether groups, and 8 to 20 carbon atoms in the hydrocarbon radical.
  • Particularly suitable are polyglycolether derivatives, in which the number of the ethyleneglycol ether groups is 5 to l5 and whose hydrocarbon radicals derive from straight-chain, primary alcohols with 12 to 18 carbon atoms or from alkyl phenols with a straightchain alkyl chain with 6 to 14 carbon atoms.
  • washing agents are obtained that are distinguished by a particularly low foaming power.
  • the builder salts are ordinarily neutral to alkaline reacting and include alkali metal triphosphates, particularly pentasodium triphosphate.
  • the triphosphates may be present also in mixtures with higher condensed phosphates, such as tetraphosphates or their hydrolysis products, such as acidic or neutral pyrophosphates.
  • the condensed phosphates may be replaced totally or partially by alkali metal salts of organic sequestering compounds, such as aminopolycarboxylic acids, particularly the alkali metal salts of nitrilotriacetic acid and ethylenediaminetetraacetic acid. Suitable are also the alkali metal salts of diethylenetriaminepentaacetic acid as well as of the higher homologs of the named aminopolycarboxylic acids.
  • homologs may be prepared, for example, by polymerization of an ester, amide or nitrile of N-acetic acid aziridine and subsequent saponification to carboxylic acid salts or by reaction of polyamines with a molecular weight of 500 to 10,000 with chloroacetic or bromoacetic acid salts in an alkaline medium.
  • suitable aminopolycarboxylic acids are poly-(Nsuccinic acid )-ethyleneimines and poly-(N-tricarballylic acid)-ethyleneimines of an average molecular weight of 500 to 500,000, that are obtainable analogous to the N-acetic acid derivatives.
  • Suitable builder salts are the sequestering, water-soluble potassium and particularly sodium salts of higher molecular weight polycarboxylic acids, for example, of polymerizates of ethylenically unsaturated mono-, diand tricarboxylic acids, such as acrylic acid, maleic acid, fumaric acid, itaconic acid, citric acid, aconitic acid, mesaconic acid and methylenemalonic acid.
  • copolymerizates of these carboxylic acids with one of each other or with other monomeric substances, able to be copolymerized therewith such as ethylenically unsaturated hydrocarbons, for example, ethylene, propylene, isobutylene and styrene with ethylenically unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, and 3- butene carboxylic acid or with other ethylenically unsaturated alcohols, ethers, esters, amides and nitriles, such as vinyl alcohol, allyl alcohol, vinylmethyl ether, acrolein, vinylacetate, acrylamide and acrylonitrile, are usable.
  • ethylenically unsaturated hydrocarbons for example, ethylene, propylene, isobutylene and styrene with ethylenically unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid
  • copolymerizates of ethylenically unsaturated mono-, di and tricarboxylic acids and polyethylenically unsaturated compounds of different structure are suitable.
  • the polymerizates and mixed polymerizates show an average degree of polymerization from 3 to 6,000 and contain, based on three monomer units, 1 to 9, preferably 2 to 9, carboxylic acid groups, capable of salt formation.
  • R is hydrogen or CH R, is hydrogen or CH:;.
  • R is hydrogen. phenyl, hydroxyl, CH CH OH,
  • X is hydrogen or COOH
  • Y is hydrogen, COOH or CH COOH, where X and Y do not both represent COOH,
  • Z is hydrogen or, if X COOH and Y H, also a is any number from to 2, and
  • b is a whole number between 3 and 6,000.
  • the value of a is not limited to whole numbers, but can be any number, that is, also fractions of whole numbers from 0 to 2.
  • organic builder salts which may be present are sequestering polyphosphonic acid salts, such as the alkali metal salts of aminopolyphosphonic acids, particularly aminotri-(methylenephosphonic acid), 1- hydroxyethane-l ,l-diphosphonic acid, methylenephosphonic acid, ethylenediphosphonic acid, and alkali .metal salts of the higher monologs of the named polyphosphonic acids. Also mixtures of the above-named sequestering agents are usable.
  • alkali metal silicates are suitable, in which the ratio of Na O:SiO is l:3.5 to 1:1.
  • alkali metals such as sodium or potassium
  • acids such as lactic acid and citric acid
  • the amount of the alkalinereacting substances, including the alkali silicates and phosphates, are to be calculated so that the pH of a usable liquor for coarse laundry is 9 to l2 for fine laundry 6 to 9.
  • bleaching agents which yield active oxygen in aqueous solutions, such as alkali metal perborates, percarbonates, perpyrophosphates and persilicates and urea perhydroperoxides, are suitable in amounts of from 0.5 to 50 percent by weight.
  • alkali metal perborates, percarbonates, perpyrophosphates and persilicates and urea perhydroperoxides are suitable in amounts of from 0.5 to 50 percent by weight.
  • sodium perborate-tetrahydrate is used.
  • the agents may contain inorganic or organic stabilizers, such as magnesium silicate, or the organic complexing agents, for instance, in amounts of from 3 to 20 percent by weight, based on the amount of perborate.
  • the so-called cold washing agent may contain bleaching activators such as tetraacetylglycoluril as an ingredient of the powder.
  • the powder particles consisting of the bleaching activator or the percompound can be coated with coating substances, such as water-soluble polymers, fatty acids or granulated salts, such as alkali metal silicates, sodium sulfate or disodium hydrogen phosphate, in order to avoid an interaction between the percompound and the activator during storage.
  • the washing agent compositions may also contain optical brighteners, particularly derivatives of diaminostilbenedisulfonic acid or their alkali metal salts, of the formula ln which X and Y are the following: NH NHCH NHCH,CH,OH, CH N-CH,CH,OH, N(CH CH,Ol-l), morpholino, dimethylmorpholino, NH C6H5, OCH3, Cl, Where X and Y may be identical or different. Particularly suitable are such compounds in which X represents an anilino and Y is a diethanolamino or morpholino group.
  • optical brighteners of the type of the diarylpyrazolines of the following formula are suitable:
  • Ar and Ar represent aryl radicals, such as phenyl, diphenyl or naphthyl that may carry other substituents, such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, sulfonic acid and sulfonamide groups or halogen atoms.
  • substituents such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, sulfonic acid and sulfonamide groups or halogen atoms.
  • a 1,3-diaryl-pyrazolone derivative is used in which the radical Ar represents a p-sulfonamid o phenyl group and the radical Ar represents a p-chlorophenyl group.
  • optical brighteners are such of the type of naphthotriazolestilbenesulfonates, ethylene-bis-benzimidazoles, ethylene-bisbenzoxazoles, thiophene-bis-benzoxazoles, dialkylaminocoumarins and cyanoanthracenes. Also mixtures of optical brighteners are usable. The optical brighteners are usually present in an amount of from 0.05 to 1.5 percent, preferably from 0.07 to 1 percent by weight.
  • the washing agent compositions may further contain enzymes from the class of the proteases, lipases and amylases or their mixtures.
  • the enzymes may be of animal or plant origin, for instance, as obtained from digestive enzymes or yeasts, such as pepsin, pancreatin, trypsin, papain, catalase and diastase.
  • enzymatic active substances are used as obtained from bacteria strains or molds, such as Bacillus subtilis and nolethers and phenolthioethers, halogenated carbanilides and salicylanilides as well as halogenated diphenylmethanes; also dyes and perfumes.
  • Liquid washing agent compositions may contain hydrotropic substances and solvents in addition, such as alkali metal salts of benzene, toluylene or xylene sulfonic acid, urea, glycerin, polyglycerin, dior trioxyethylene glycol, polyoxyethylene glycol, ethanol, ipropanol and ether alcohols.
  • solvents such as alkali metal salts of benzene, toluylene or xylene sulfonic acid, urea, glycerin, polyglycerin, dior trioxyethylene glycol, polyoxyethylene glycol, ethanol, ipropanol and ether alcohols.
  • washing agent compositions may also contain known foam inhibitors, such as saturated fatty acids with 20 to 24 carbon atoms, or their alkali metal soaps, higher molecular weight fatty acid esters or triglycerides or trialkylmelamines.
  • foam inhibitors such as saturated fatty acids with 20 to 24 carbon atoms, or their alkali metal soaps, higher molecular weight fatty acid esters or triglycerides or trialkylmelamines.
  • the qualitative and quantitative composition of these washing agents depends largely upon their field of application.
  • the content of polyester salts in the compounded washing agents amounts to 0.1 to 20 percent, preferably 0.2 to percent by weight.
  • the difference of 80 to 99.1 percent, preferably 90 to 99.8 percent by weight, is the other washing agent ingredients, whose quantitative composition may correspond to the following scheme (data in percent by weight):
  • the surface-active compounds may consist up to 100 percent, preferably 5 to 70 percent, of compounds of the sulfonate and/or sulfate type, up to 100 percent, preferably 5 to 40 percent of non-ionic compounds of the polyglycol ether type and up to 100 percent, preferably ID to 50 percent of soap.
  • the builder salts may be composed up to 100 percent, preferably 25 to 95 percent, of alkali metal triphosphates and their mixtures with alkali metal pyrophosphates, up to 100 percent, preferably 5 to 50 percent, of an alkali metal salt of a sequestering agent from the class of the polyphosphonic acids, nitrilotriacetic acid, ethylenediaminetetraacetic acid, and up to 100 percent, preferably 5 to 75 percent, of at least one compound from the class of the alkali metal silicates, alkali metal carbonates, and alkali metal borates.
  • the optical brighteners particularly the foam inhibitors, which may be present in the agents of the invention in amounts of from 0 up to 5 percent, preferably in amounts of 0.2 to 3 percent
  • the enzymes that may be present in an amount of from 0 up to 5 percent, preferably 0.2 to 3 percent.
  • carboxymethylcellulose whose share may be from 0 up to 5 percent
  • I l O T preferably 0.2 to 3 percent, all by weight of the total composition.
  • the washing agent compositions of the invention are utilized in amounts of from 0.4 gm to-8.0 gm per liter in an aqueous washing liquor bath.
  • the washing of the soiled textiles is conducted at temperatures of from 20 to C for a time sufficient to clean the textiles.
  • the share of the polyester sulfonates containing quaternary ammonium compounds usually amounts to from 0.005 to l gm/liter.
  • the close to practice dirt-skin fat combination used for the soiling of the cotton yarn, consists of a mixture 'of kaolin, iron oxide black, soot and synthetic skin fat (from l/3 fatty acids, 1/3 fat and H3 hydrocarbons).
  • the cotton yarn contains after soiling about 1 1 percent of pigments and about 2 percent skin fat.
  • a washing agent of the following composition (in percent by weight) was compounded:
  • the application concentration of the washing agents was 5 gm/liter, the water hardness 10 dH (degrees German hardness).
  • the textile samples of the synthetic fabric and the mixed fabrics of finished cotton and synthetic fiber were washed at 40 to 60 C, the samples of finished cotton at 95 C.
  • the weight ratio of textile goods to washing liquor was 1:30 or 1:12, as indicated.
  • After a washing time of minutes the textile samples were rinsed four times with distilled water.
  • After three washings the degree of whiteness of the samples was determined by photometer. For comparison wash tests without greying inhibitor were
  • the preceding specific embodiments are illustrative of the practice of the invention. it is to be understood, however, that other expedients known to those skilled in the art, or disclosed herein, may be employed without departing from the spirit of the invention or the scope of the appended claims.
  • Me represents a metal selected from the gfc J u p misi ing of sodium and potassium, n represents the integers 2, 3 or 4, and x represents a whole number from 5 to 5,000.
  • R represents a hydrocarbon with 6 to 24 carbon atoms selected from the group consisting of alkyl, alkenyl, phenyl, phenylalkyl, alkylphenyl, cycloalkyl, cycloalkylalkyl and alkylcycloalkyl and R represents a hydrocarbon with 1 to 10 carbon atoms selected from the group consisting of alkylene, alkenylene, phenylene, alkylphenylene, cyclohexylene and cyclohexenylene.
  • R represents a straight-chained alkyl with 10 to 20 carbon atoms.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Detergent Compositions (AREA)
US00369076A 1970-11-04 1973-06-11 Polyester salts containing quaternary ammonium groups Expired - Lifetime US3816378A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DE19702054097 DE2054097A1 (de) 1970-11-04 1970-11-04 Zur Verwendung in Waschmitteln geeignete, quartäre Ammoniumgruppen enthaltende Polyestersalze
NL7113785A NL7113785A (cs) 1970-11-04 1971-10-07
AT947371A AT314052B (de) 1970-11-04 1971-11-03 Waschmittel mit einem Gehalt an quartäre Ammoniumgruppen enthaltende Polyestersalzen
CH1601271A CH562317A5 (cs) 1970-11-04 1971-11-03
FR7139526A FR2112453B1 (cs) 1970-11-04 1971-11-04
US00369076A US3816378A (en) 1970-11-04 1973-06-11 Polyester salts containing quaternary ammonium groups

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19702054097 DE2054097A1 (de) 1970-11-04 1970-11-04 Zur Verwendung in Waschmitteln geeignete, quartäre Ammoniumgruppen enthaltende Polyestersalze
US18894071A 1971-10-13 1971-10-13
US00369076A US3816378A (en) 1970-11-04 1973-06-11 Polyester salts containing quaternary ammonium groups

Publications (1)

Publication Number Publication Date
US3816378A true US3816378A (en) 1974-06-11

Family

ID=27182975

Family Applications (1)

Application Number Title Priority Date Filing Date
US00369076A Expired - Lifetime US3816378A (en) 1970-11-04 1973-06-11 Polyester salts containing quaternary ammonium groups

Country Status (6)

Country Link
US (1) US3816378A (cs)
AT (1) AT314052B (cs)
CH (1) CH562317A5 (cs)
DE (1) DE2054097A1 (cs)
FR (1) FR2112453B1 (cs)
NL (1) NL7113785A (cs)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3873603A (en) * 1970-11-04 1975-03-25 Henkel & Cie Gmbh Polyester sulfonates containing quaternary ammonium groups
US4137245A (en) * 1975-07-22 1979-01-30 The Miranol Chemical Company, Inc. Nitrogenous condensation products
EP0144975A3 (en) * 1983-12-14 1985-07-31 Hoechst Aktiengesellschaft Quaternised alkoxylated polyesters, process for their preparation and their use
US4730079A (en) * 1985-07-25 1988-03-08 Hoechst Aktiengesellschaft Quaternary oxalkylated polycondensates
US5913972A (en) * 1996-04-22 1999-06-22 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Aqueous pigment dispersion, water-soluble resin, production process of the resin, and equipment suitable for use with the dispersion
US6174965B1 (en) * 1998-02-25 2001-01-16 Kansai Paint Company, Limited Polyester resin, process for its production and its use
WO2012071313A1 (en) * 2010-11-24 2012-05-31 The Lubrizol Corporation Polyester quaternary ammonium salts
WO2012071305A1 (en) * 2010-11-23 2012-05-31 The Lubrizol Corporation Polyester quaternary ammonium salts

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3873603A (en) * 1970-11-04 1975-03-25 Henkel & Cie Gmbh Polyester sulfonates containing quaternary ammonium groups
US4137245A (en) * 1975-07-22 1979-01-30 The Miranol Chemical Company, Inc. Nitrogenous condensation products
EP0144975A3 (en) * 1983-12-14 1985-07-31 Hoechst Aktiengesellschaft Quaternised alkoxylated polyesters, process for their preparation and their use
US4730079A (en) * 1985-07-25 1988-03-08 Hoechst Aktiengesellschaft Quaternary oxalkylated polycondensates
US5913972A (en) * 1996-04-22 1999-06-22 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Aqueous pigment dispersion, water-soluble resin, production process of the resin, and equipment suitable for use with the dispersion
AU724924B2 (en) * 1996-04-22 2000-10-05 Dainichiseika Color & Chemicals Mfg. Co. Ltd. Aqueous dispersion of pigment and sulphonated polyester dispersant
US6174965B1 (en) * 1998-02-25 2001-01-16 Kansai Paint Company, Limited Polyester resin, process for its production and its use
WO2012071305A1 (en) * 2010-11-23 2012-05-31 The Lubrizol Corporation Polyester quaternary ammonium salts
WO2012071313A1 (en) * 2010-11-24 2012-05-31 The Lubrizol Corporation Polyester quaternary ammonium salts
CN103328537A (zh) * 2010-11-24 2013-09-25 卢布里佐尔公司 聚酯季铵盐
CN103328537B (zh) * 2010-11-24 2015-05-27 路博润公司 聚酯季铵盐

Also Published As

Publication number Publication date
CH562317A5 (cs) 1975-05-30
DE2054097A1 (de) 1972-05-10
AT314052B (de) 1974-03-25
FR2112453A1 (cs) 1972-06-16
FR2112453B1 (cs) 1975-04-18
NL7113785A (cs) 1972-05-08

Similar Documents

Publication Publication Date Title
EP0042187B2 (en) Detergent composition containing low level of substituted polyamines
US3676338A (en) Detergent compositions containing a textile softener
US3726797A (en) Detergent compositions and processes incorporating n-(2-hydroxy hydrocarbyl)iminodicarboxylates
US3650962A (en) Washing bleaching and cleansing agents containing poly-(n-acetic acid)-ethyleneimines
US3965024A (en) Washing agent compositions and washing assistant composition containing phosphonopolycarboxylate sequestering agents
US4612352A (en) Water-soluble or water-dispersible graft polymers, their preparation and their use
AU710487B2 (en) N-acyl ethylenediaminetriacetic acid surfactants as enzyme compatible surfactants, stabilizers and activators
JPH0415840B2 (cs)
US3663444A (en) Washing and cleansing agents with polyamides having improved dirtcarrying capacity
US3850832A (en) Washing, rinsing and cleansing agent compositions containing furan-maleic anhydride copolymer sequestering agents
US3897347A (en) Washing agents containing a textile softener and process of washing and softening textiles
JPH09500633A (ja) 漂白用アミドペルオキシカルボン酸
US3737385A (en) Washing,bleaching and cleansing agents containing poly-(n-alkyl-dicarboxylic acid)-alkyleneimines
US3816378A (en) Polyester salts containing quaternary ammonium groups
US3640874A (en) Bleaching and detergent compositions
US4927559A (en) Low perborate to precursor ratio bleach systems
US3803036A (en) Detergent-softener compositions containing sulfosuccinates of polyhydroxy tertiary amines
US3718597A (en) Washing, bleaching and cleansing agents containing copolymeric n-alkylcarboxylic acid alkyleneimines
US3650963A (en) Washing bleaching and cleansing agents containing poly-(n-acetic acid)-ethyleneimines
US3751370A (en) Low-foaming rinsing washing and cleaning compositions
US3708427A (en) Washing and cleansing compositions
US3609090A (en) Built detergent compositions containing hydroxy ether sulfonates
US3873603A (en) Polyester sulfonates containing quaternary ammonium groups
DE2165900A1 (de) Waschmittel mit einem gehalt an vergrauungsverhuetenden zusaetzen
US4009110A (en) Copolymers of maleic anhydride, diketene and alkyl ethers, process for their manufacture and their use